Color photographic light-sensitive material containing silver occlusion preventing agent

ABSTRACT

WHEREIN R1 represents hydrogen or methyl, R2 represents hydrogen, methyl, ethyl, propyl or butyl, R3 represents hydrogen, methyl, ethyl, propyl and x/y varies from 95/5 to 20/80.   A color photographic silver halide light-sensitive material comprising a support having a silver halide light-sensitive emulsion layer thereon wherein a copolymer is incorporated in said light-sensitive emulsion layer or a non-light-sensitive auxiliary layer on said support, said copolymer being represented by the following formula:

United States Patent Yasuda et al.

[151 3,655,389 [4 1 Apr. 11, 1972 [72] Inventors: Yukio Yasuda; NobuoTsuji; Takushi Miyazako, all of Kanagawa, Japan [73] Assignee: FujiPhoto Film Co., Ltd., Kanagawa,

Japan [22] Filed: Sept. 22, 1970 [2]] Appl. No.: 74,521

[30] Foreign Application Priority Data Sept, 22, 1969 Japan ..44/75465[52] U.S. Cl ..96/100, 96/114 [51] Int. Cl ..G03c H40 [58] FieldofSearch ..96/114, 100

[56] References Cited UNITED STATES PATENTS 2,495,918 1/1950 Bolton..96/114 3,360,373 12/1967 Shaller et al ..96/114 FOREIGN PATENTS ORAPPLICATIONS 1,052,487 12/1966 Great Britain ..96/1 14 PrimaryExaminer-Ronald H. Smith Att0rneySughrue, Rothwell, Mion, Zinn andMacpeak ABSTRACT A color photographic silver halide light-sensitivematerial comprising a support having a silver halide light-sensitiveemulsion layer thereon wherein a copolymer is incorporated in saidlight-sensitive emulsion layer or a non-light-sensitive auxiliary layeron said support, said copolymer being represented by the followingformula:

wherein R represents hydrogen or methyl, R represents hydrogen, methyl,ethyl, propyl or butyl, R represents hydrogen, methyl, ethyl, propyl orbutyl and x/y varies from 95/5 to 20/80.

12 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of theInvention This invention relates to a color photographic light-sensitivematerial. More particularly, it relates to a color photographiclight-sensitive material of improved silver bleaching property.

2. Description of the Prior Art One of the difficulties encountered inthe processing of -a color photographic material is the phenomenon thatsilver bleaching is not complete. This is a serious problem,particularly in the case of a color photographic light-sensitivematerial using an oil-soluble coupler as disclosed in U.S. Pat. No.2,322,027.

When a color photographic light-sensitive material is subjected toexposure and then to color development, a color image and a silver imageare formed. The silver image is then removed by a silver bleachingtreatment and a fixing treatment, thus obtaining only a dye image. Ifthe step of silver bleaching is incomplete, however, a part of thesilver image remains in the material. Such an occluded silver cloudmakes the color photographic image obscure and remarkably degrades thecolor reproduction.

Some methods have been proposed in order to improve the silver bleachingproperty. It is well known to incorporate some compounds in a colorphotographic light-sensitive material for the purpose of preventing suchsilver occlusion. For example, a polymer containing vinylpyrrolidone isdescribed as a silver occlusion inhibitor in British Pat. No. 1,052,487.However, the compound described in this patent has the disadvantage thatthe development of exposed silver halide grains is markedly suppressedso that a long time is necessary for development, although it has aneffect of improving the silver removal.

It is the principal object of the present invention to prevent silverocclusion without suppressing the development in a color photographiclight-sensitive material, in particular, containing an oil-solublecoupler.

SUMMARY OF THE INVENTION The above-mentioned object can be accomplishedby incorporating in a color photographic light-sensitive material acopolymer of 2-(N-acyl)aminoethyl acrylate or 2-(N- acyl)aminoethylmethacrylate and N-vinylpyrrolidone.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with the presentinvention, therefore, there is provided a color photographiclight-sensitive material in which in a light-sensitive emulsion layer orin a non-light-sensitive auxiliary layer is incorporated a copolymerrepresented C l-l C H,, or C I-I and x/y=95/5-20/80. Thenon-lightsensitive auxiliary layer is a layer adjacent to thelight-sensitive emulsion layer, for example, a protective layer, anintermediate layer, a filter layer or antihalation layer.

The effect of the copolymer of N-vinylpyrrolidone and 2- (N-acyl)aminoethyl acrylate or 2-(N-acyl)aminoethyl methacrylate depends on itsmonomer ratio. The effect of improving the silver removing propertyincreases with an in crease in the amount (y) of N-vinylpyrrolidone,whereas the development suppressing property decreases with the decreaseof (y). Accordingly, acopolymer having an x/y ratio of /5 to 20/80, inparticular 90/10 to 40/60, is preferably used.

The effect of the copolymer-of the present invention is substantiallyindependent from the degree of polymerization of the copolymer.Therefore, any copolymer capable of being dissolved or dispersed incolloidal state in water or aqueous alkaline solution can be usedindependently of its degree of polymerization.

The copolymer of the present invention, represented by the formula (I),is obtained by polymerizing, in a solvent, vinylpyrrolidone and amonomer represented by the formula:

1 CH I J R7 70 O CHzCHnNf in which R R and R have the same meaning as informula (I). A suitable solvent is water or dimethylformamide. Potassiumpersulfate, hydrogen peroxide or azobisisobutyronitrile may be used as apolymerization initiator. Furthermore, isopropanol may be used so as tocontrol the degree of polymerization.

Synthesis of a monomer represented by formula (II) may be carried out bythe reaction of (l) 2-(N-acyl)aminoethyl alcohol with acrylic acid ormethacrylic acid, (2) the alcohol with acrylic chloride or methacrylicchloride, (3) the alcohol with ,B-propiolactone or (4) the alcohol withacrylic acid ester or methacrylic acid ester.

Synthetic examples of the copolymer used in the invention are asfollows:

Synthetic Example 1 a. Synthesis of 2-(N-formyl-N-methyl)aminoethylacrylate 52 g of 2-(N-formyl-N-methyl)aminoethyl alcohol was chargedinto a flask of 500 ml equipped with a stirrer with g of triethylamine,200 ml of acetone and 1.5 g of hydroquinone as a polymerizationinhibitor and, while keeping the temperature at 5 C. and stirring, 46 gof acrylic chloride was dropwise added. After the reaction, the salt wasremoved and l g of hydroquinone was added followed by distillation. Thecompound obtained had the following structure which was identified byelementary analysis, NMR, mass spectrometry and infrared spectrum.

Yield: 63.2 g (81.0%)

B.P.: 102l04 C./0.5 mm. Hg Analysis for C H N0 (molecular weight:157.17)

c H N calculated 53.49 7.05 8.91 found 53.1 7.2 8.4

b. Synthesis of a copolymer of 2-(N-formyl-N- methyl)aminoethyl acrylateand N-vinylpyrrolidone Synthetic Example 2 a. Synthesis of2-(N-acetyl)aminoethyl acrylate 76 g of 2- (N-acetyDaminoethyl acrylatewas charged into a 1,000 ml flask equipped with a stirrer along with 250ml of acetone, 150 g of triethylamine and 1.5 g of hydroquinone as apolymerization inhibitor, and then 68 g of acrylic chloride was addedthereto dropwise while stirring and keeping the reaction temperaturelower than 10 C. After being allowed to stand for one night, thetriethylamine hydrochloride was filtered off and the reaction mixturewas then distilled under reduced pressure. The compound obtained had thefollowing structure which was identified by elementary analysis, NMR andinfrared spectrum.

Yield: 78 g (66%) COCHs CHQ=CHC O O (CH )zN\ Analysis for C H NO(molecular weight: 157.17)

c H N calculated 53.49 7.05 8.91 found 53.9 6.9 8.5

b. Synthesis of a copolymer of 2-( N-acetyl)aminoethyl acrylate andN-vinylpyrrolidone (monomer ratio: 8 2) 31.4 g of Z-(N-acetyl)aminoethyl acrylate, 5.6 of N-vinylpyrrolidone, 200 ml of water, 2 ml of30 percent aqueous ammonia, 0.3 ml of isopropanol and 185 mg ofpotassium persulfate as a polymerization initiator were charged into aflask of 300 ml equipped with a stirrer, rinsed with nitrogen andstirred at 60 C for 2 hours to effect polymerization. After thereaction, the solution was subjected to dialysis in a dialysis membranefor one night and then to freeze drying.

Yield: 35.8 g (96.8%)

The quantity to be added of the copolymer used in the present inventiondepends on its properties, the variety of layers into which it is addedand, the variety and quantity of the coupler and other additives. In thecase of adding the copolymer to a light-sensitive emulsion layer, goodresults can generally be obtained by employing about 5 percent by weightof the copolymer based on the weight of the binder. Ordinarily, 1-5percent by weight is preferred since the color-forming efficiency andphysical properties of the layer decrease when the addition quantityexceeds 20 percent by weight. In the case of adding the copolyer to anon-light-sensitive auxiliary layer, on the other hand, even an additionof 50 percent by weight, based on the weight of the binder of thecopolymer, does not lower the color forming efficiency and physicalproperties of the layer.

The copolymer of the present invention may be added to a dispersionduring the dispersing of the coupler or it may be added with otheradditives during the preparation of a coating solution.

As a binder for the emulsion used in the color photographiclight-sensitive material of the present invention, a suitable protectivecolloid may be used, for example, gelatin, polyvinyl alcohol or itsderivative, polyacrylamide or its derivative, cellulose derivative,casein or alginate. Gelatin is most suitable.

The following examples are provided to further illustrate the presentinvention in detail without limiting the same.

EXAMPLE l ml of a 5 percent aqueous solution of Z-(N-acetyl-N-methyl)aminoethyl acrylate N-vinylpyrrolidone copolymer (monomer ratio:6 4) was added to 20 ml of a 10 percent aqueous solution of gelatincontaining 2 ml of a 10 percent aqueous solution of sodiumalkylbenzenesulfonate. Then, 3.0 g of4-benzoylacetamide-N-butyl-N-octylbenzamide, dissolved by heating in 2.0ml of dibutyl phthalate, and 3.0 ml of ethyl acetate were added theretoas a yellow coupler and stirred vigorously at 40-50 C. for 15 minutes bymeans of a homoblender, to thus obtain a coupler dispersion. All of thedispersion was mixed with a photographic emulsion containing 7.0 g ofsilver bromide and 5.0 g of gelatin and coated onto a film base followedby drying. The resulting light-sensitive material was exposed andsubjected to the following treatments at 24 C.

Color development I l min. rinsing 1/4 min. fixing 2 min. water washing1 min. bleaching 6 minv water washing 2 1/2 min. fixing 2 min. waterwashing 6 min. The treating solutions had the following composition:

Color development solution sodium hexametaphosphate 2 g. sodium sult'tte(anhydrous) 4 gv Z-methyl-4-N, N-diethylaniline sulfate 3 g. sodiumcarbonate (monohydrate) 20 g. potassium bromide 2 g. water to make Iliter Fixing solution sodium thiosulfate (anhydrous) 153 g. sodiumsulfite (anhydrous) l5 g. acetic acid 48 g. boric acid 7.5 g. potassiumalum l5 g. water to make 1 liter Bleaching solution potassium bromide 20g. potassium bichromate 5 g. potassium alum 40 g. pH adjusted to 3.1with sulfuric acid water to make 1 liter In the resulting film,bleaching of silver was completely carried out with only a yellow colorimage remaining while in the same film but free from the copolymer,bleaching of silver was incomplete and there was a color image of yellowwith a cloud of silver. The optical density of the two films wasmeasured by a red light substantially free from absorption of the yellowimage. As is evident from the results as shown in Table l, the filmcontaining no copolymer gives a high optical density due to theabsorption of silver.

TABLE 1 Presence of Copolymer Optical Density Yes 0.1 i No 053Substantially similar results were also obtained in the case of using anaqueous solution containing g of potassium ferricyanide per 1 liter as ableaching solution.

EXAMPLE 2 The same procedure as in Example l was repeated except that4.3 g ofl-(2,4,6-trichlorophenyl)-3-(3-(N-butyltetradecaneamide)-propaneamide)pyrazoline-S-on was used as a magenta coupler in place of the yellowcoupler of Example l and a copolymer of 2-(N-formyl-N-methyl)-aminoethylmethacrylate and N-vinylpyrrolidone (monomer ratio: 6 4) was used as thecopolymer. In the copolymer-free film, a color image of magenta waspresent together with a cloud of silver and was considerably obscure.The optical density of the two films was measured by a red lightsubstantially free from absorption of the color image of magenta. As isevident from the results shown in Table 2, the film containing nocopolymer gives a high optical density due to the absorption of silver.

The same procedure as in Example 1 was repeated except that 2.4 g ofl-hydroxy-4-chlor -2-N-dodecylnaphthamide was used as a cyan coupler inplace of the yellow coupler of Example 1 and a copolymer of2-(N-formyl-N- methyl)aminoethyl acrylate and N-vinylpyrrolidone(monomerratio: 6 4) was used as the copolymer. In the copolymer-free film, acolor image of cyan was present together with a cloud of silver and wasconsiderably obscure. The optical density of the two films was measuredby a blue light substantially free from absorption of the color image ofcyan. As is evident from the results shown in Table 3, the filmcontaining no copolymer gives a high optical density due to theabsorption of silver.

TABLE 3 Presence of Copolymer Optical density Yes 0.4] No 081 EXAMPLE 4The same procedure as in Example 1 was repeated except that three kindsof copolymers of 2-(n-acetyl)aminoethyl acrylate andN-vinyl-pyrrolidone, differing in monomer ratio, were used. As isevident from the results shown in Table 4, the film containing thecopolymer gives a lower red optical density than the film containing nocopolymer.

This example is given for the illustration of the fact that thecopolymer of the present invention has a low suppressing action ofdevelopment. The ratio of optical densities when a film is exposed anddeveloped for 3 minutes and for minutes was compared for the filmscontaining the copolymers of Examples l to 4 and comparison filmsprepared in a manner similar to that of Example 1 but using copolymersof N-vinylpyrrolidone and vinyl acetate (monomer ratio: 7 3), and N-vinylpyrrolidone and sytrene (monomer ratio: 7 3). The larger thisvalue, the less the suppressing action of development. As is evidentfrom the results shown in Table 5, the copolymers of the presentinvention give less of a suppressing action of development as comparedwith the known copolymers.

TABLE 5 Copolymer Density ratio copolymer ofZ-NmcetyLN-methyl)aminoethyl n if acrylate and N-vinylpyrrolidone(monomer ratio: 6 :4) 0.57 copolymer of 2-(N-formyl-N-methyl)aminoethylmethacrylate and N-vinylpyrrolidone (monomer ratio: 6 :4) 0.52 copolymerof 2-(N-formyl-N-methyl)aminoethyl acrylate and N-vinylpyrrolidone(monomer ratio: 6 4) 0.50 copolymer of 2-( N-acetyl)aminoethyl acrylateand N- vinylpyrrolidone (monomer ratio: 8 Z) 0.49 copolymer ofZ-(N-acetylaminoethyl acrylate and N-vinylpyrrolidone (monomer ratio: 73) 0.43 copolymer of 2-( N-acetyl)aminoethyl acrylate andN-vinylpyrrolidone (monomer ratio: 4 6) 0.35 copolymer ofN-vinylpyrrolidone and vinyl acetate (monomer ratio: 7 3) 0.23 copolymerof N-vinylpyrrolidone and styrene (monomer ratio: 7 3) 0.25 none 0.55

EXAMPLE 6 To 1 kg of a photographic emulsion containing 60 g of silverbromide and 60 g of gelatin was added 15 ml of a 2 percent (by weight)aqueous solution of a copolymer of Z-(N-acetyl- N-methyl)aminoethylacrylate and N-vinylpyrrolidone (monomer ratio: 9 l). A copolymer-freecoupler dispersion prepared by a procedure similar to that of Example 1was added thereto, coated onto a film base and dried. For comparison,another film was prepared by the same procedure as mentioned above butusing no copolymer. The two films were processed as in Example 1 andtheir red optical density was measured. As is evident from the resultsshown in Table 6, the film containing the copolymer of the inventiongives a lower red optical density.

TABLE 6 Presence of Copolymer Red optical density Yes 0. l 7 No 0.54

wherein R represents hydrogen or methyl, R represents hydrogen, methyl,ethyl, propyl or butyl, R represents hydrogen, methyl, ethyl, propyl orbutyl and x/y varies from /5 to 20/80.

2. The color photographic light-sensitive material as claimed in claim 1wherein said copolymer is incorporated in the light sensitive emulsionlayer in an amount of up to 20 percent by weight, based on the weight ofthe binder of said layer.

3. The color photographic light-sensitive material of claim 2 whereinthe amount of said copolymer varies from 1 to 5 percent, by weight,based on the weight of binder.

4. The color photographic light-sensitive material as claimed in claim 1wherein said copolymer is incorporated in a nofi-light-sensitiveauxiliary layer in an amount of up to 50 percent by weight based on theweight of the binder of said layer.

5. The color photographic light-sensitive material as A rolidone of amonomer ratio of 6 4.

9. The color photographic light-sensitive material as claimed in claim 1wherein said copolymer is a copolymer of2-(N-forrnyl-N-methyl)aminoethyl methacrylate and N-vinylpyrrolidone ofa monomer ratio of 6 4.

10. The color photographic light-sensitive material as claimed in claim1 wherein said copolymer is a copolymer of 2-(N-acetyl)amino-ethylacrylate and N-vinylpyrrolidone of a monomer ration of 8 2.

rolidone of a monomer ration of 9 l.

2. The color photographic light-sensitive material as claimed in claim 1wherein said copolymer is incorporated in the light sensitive emulsionlayer in an amount of up to 20 percent by weight, based on the weight ofthe binder of said layer.
 3. The color photographic light-sensitivematerial of claim 2 wherein the amount of said copolymer varies from 1to 5 percent, by weight, based on the weight of binder.
 4. The colorphotographic light-sensitive material as claimed in claim 1 wherein saidcopolymer is incorporated in a non-light-sensitive auxiliary layer in anamount of up to 50 percent by weight based on the weight of the binderof said layer.
 5. The color photographic light-sensitive material asclaimed in claim 1 wherein x/y varies from 90/10 to 40/60.
 6. The colorphotographic light-sensitive material as claimed in claim 1 wherein saidcopolymer is a copolymer of 2-(N-formyl-N-methyl) aminoethyl acrylateand N-vinylpyrrolidone of a monomer ratio of 6 :
 4. 7. The colorphotographic light-sensitive material as claimed in claim 1 wherein saidcopolymer is a copolymer of 2-(N-acetyl)aminoethyl acrylate andN-vinylpyrrolidone of a monomer ratio of 4 :
 6. 8. The colorphotographic light-sensitive material as claimed in claim 1 wherein saidcopolymer is a copolymer of 2-(N-acetyl-N-methyl)aminoethyl acrylate andN-vinylpyrrolidone of a monomer ratio of 6 :
 4. 9. The colorphotographic light-sensitive material as claimed in claim 1 wherein saidcopolymer is a copolymer of 2-(N-formyl-N-methyl)aminoethyl methacrylateand N-vinylpyrrolidone of a monomer ratio of 6 :
 4. 10. The colorphotographic light-sensitive material as claimed in claim 1 wherein saidcopolymer is a copolymer of 2-(N-acetyl)amino-ethyl acrylate andN-vinylpyrrolidone of a monomer ration of 8 :
 2. 11. The colorphotographic light-sensitive material as claimed in claim 1 wherein saidcopolymer is a copolymer of 2-(N-acetyl)aminoethyl acetate andN-vinylpyrrolidone of a monomer ration of 7 :
 3. 12. The colorphotographic light-sensitive material as claimed in claim 1 wherein saidcopolymer is a copolymer of 2-(N-acetyl-N-methyl)aminoethyl acrylate andN-vinylpyrrolidone of a monomer ration of 9 : 1.